HK1093351B - Disperse azo dyestuffs - Google Patents

Description

Disperse azo dyes

The present invention relates to the field of disperse dyes.

Disperse dyes containing cyanomethyl ester groups are known from the literature and are described, for example, in GB 909,843, DE-A2130992, GB 1,457,532, GB 1,536,429, FR-A1,531,147, US3,776,898, JP 55161857, GB 2,104,088, EP 0685531A 1 and WO 95/20014.

The inventors of the present invention have surprisingly found that if a selected dye containing one cyanomethyl ester group as defined below is used, a dye on a polyester with good moisture resistance can be obtained.

The invention claims the dyes of formula I

Wherein

D is a radical of the formula (Ila) or a radical of the formula (IIb) or a radical of the formula (IIc) or a radical of the formula (IId) or a radical of the formula (IIe)

Wherein

T¹、T²And T³Independently hydrogen, halogen or nitro;

T⁴is hydrogen, halogen, cyano or nitro;

wherein T is¹、T²、T³And T⁴At least one of which is not hydrogen;

wherein

T⁵Is hydrogen or halogen; and

T⁶is hydrogen, -SO₂CH₃-SCN or nitro;

wherein T is⁵And T⁶At least one of which is not hydrogen;

wherein T is⁷Is nitro, -CHO or formula

In which T is¹⁰is-H, halogen, nitro and cyano;

T⁸is hydrogen or halogen; and

T⁹is nitro, cyano or-COCH₃or-COOT¹⁰Wherein T is¹⁰Is (C)₁-C₄) -an alkyl group;

R¹is hydrogen, (C)₁-C₄) -alkyl or-NHCOR⁶Wherein R is⁶Is (C)₁-C₄) -alkyl or phenyl;

R²is unsubstituted (C)₁-C₆) Alkyl, substituted (C)₁-C₆) -alkyl, benzyl or phenethyl;

R³is hydrogen or methyl;

R⁴is hydrogen or methyl;

R⁵is hydrogen, methyl or phenyl;

R⁷is hydrogen, chlorine, methoxy or ethoxy;

n is 0, 1 or 2;

s is 0 or 1;

provided that

At R¹、R³、R⁴、R⁵And R⁷Is hydrogen and n is 0

D is a radical of the formula (IIc), (IId), (IIe) or (Ila), where T¹Not being nitro radicals

If T is²、T³And T⁴Is a hydrogen atom, and is,

if T is²And T³Is hydrogen and T⁴Is chloro or cyano and

if T is²And T⁴Is hydrogen and T³Is chlorine; and

further provided that

R²Is unsubstituted (C)₁-C₆) Alkyl if RT¹Is methyl, R³、R⁴、R⁵And R⁷Is hydrogen and n ═ 0.

Represents R¹、R⁶Or T¹⁰The alkyl group of (a) may be straight-chain or branched, and is preferably methyl, ethyl, n-propyl, isopropyl or n-butyl. Represents R²The same is true of alkyl groups of (2), which may also be pentyl or hexyl. Represents R²The substituted alkyl group of (C) is preferably substituted by hydroxy₁-C₄) -alkoxy or halogen substitution.

Represents T¹、T²、T³、T⁴、T⁵Or T⁸The halogen of (a) is preferably chlorine or bromine.

Preferred examples of D are derived from the following amines:

2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2-chloro-4-nitroaniline, 4-chloro-2-nitroaniline, 2-bromo-4-nitroaniline, 2, 6-dichloro-4-nitroaniline, 2, 6-dibromo-4-nitroaniline, 2-chloro-6-bromo-4-nitroaniline, 2, 5-dichloro-4-nitroaniline, 2-cyano-6-bromo-4-nitroaniline, 2-cyano-6-chloro-4-nitroaniline, 2, 4-dinitroaniline, 2-chloro-4, 6-dinitroaniline, 2-bromo-4, 6-dinitroaniline, 2, 6-dicyano-4-nitroaniline, 2-cyano-4, 6-dinitroaniline, 2-amino-5-nitrothiazole, 2-amino-3, 5-dinitrothiophene, 2-amino-3-ethoxycarbonyl-5-nitrothiophene, 2-amino-3-acetyl-5-nitrothiophene, 2-amino-3-cyano-4-chloro-5-formylthiophene, 7-amino-5-nitrobenzoisothiazole, 2-amino-6-nitrobenzothiazole, 2-amino-6-methanesulfonylbenzothiazole; 2-amino-6-thiocyanobenzothiazole, 2-amino-5, 6-dichlorobenzothiazole and 2-amino-6, 7-dichlorobenzothiazole (mixture).

Preferred disperse dyes of the present invention are those of the formula (la)

Wherein

D is a group of formula (Ila), (Ilb), (llc), (Ild) or (IIe);

R¹is (C)₁-C₄) -an alkyl group;

R²is unsubstituted (C)₁-C₆) -alkyl, benzyl or phenethyl; and

n is 0, 1 or 2.

In particularly preferred dyes of the formula (la), R¹Is methyl, R²Is ethyl and n is 0.

Preferred further disperse dyes according to the invention are those of the formula (Ib)

Wherein

T³Is bromine or chlorine; and

R²is unsubstituted (C)₁-C₆) Alkyl, substituted (C)₁-C₆) -alkyl, benzyl or phenethyl;

in particularly preferred dyes of the formula (Ib), R²Is ethyl, benzyl or phenethyl.

Still other disperse dyes preferred in the present invention are of formula (Ic)

Wherein

D is a radical of the formula (IIa), (IIb), (IIc), (IId) or (IIe);

R¹is hydrogen, (C)₁-C₄) -alkyl or-NHCOR⁶Wherein R is⁶Is (C)₁-C₄) -alkyl or phenyl;

R²is unsubstituted (C)₁-C₆) Alkyl, substituted (C)₁-C₆) -alkyl, benzyl or phenethyl; and

R³is hydrogen and R⁴Is methyl or R³Is methyl and R⁴Is hydrogen.

Still other disperse dyes preferred for the present invention are of the formula (Id)

Wherein

D is a radical of the formula (IIa), (IIb), (IIc), (IId) or (IIe);

R¹is hydrogen, (C)₁-C₄) -alkyl or-NHCOR⁶Wherein R is⁶Is (C)₁-C₄) -alkyl or phenyl;

R²is unsubstituted (C)₁-C₆) Alkyl, substituted (C)₁-C₆) -alkyl, benzyl or phenethyl; and

R⁵is methyl or phenyl;

still other disperse dyes preferred according to the invention are of formula (Ie).

Wherein

D is a radical of the formula (IIa), (IIb), (IIc), (IId) or (IIe);

R²is unsubstituted (C)₁-C₆) Alkyl, substituted (C)₁-C₆) -alkyl, benzyl or phenethyl;

R⁶is (C)₁-C₄) -alkyl or phenyl;

R⁷is chloro, methoxy or ethoxy; and

n is 0, 1 or 2.

Still other disperse dyes preferred in the present invention are of the formula (If)

Wherein

R²Is unsubstituted (C)₁-C₆) Alkyl, substituted (C)₁-C₆) -alkyl, benzyl or phenethyl;

R⁸is a nitro group; and

n is 0, 1 or 2;

still other disperse dyes preferred in the present invention are of the formula (Ig)

Wherein

D is a radical of the formula (IIa), (IIb), (IIc), (IId) or (IIe);

R¹is hydrogen, (C)₁-C₄) -alkyl or-NHCOR⁶Wherein R is⁶Is (C)₁-C₄) -alkyl or phenyl;

R²is unsubstituted (C)₁-C₆) Alkyl, substituted (C)₁-C₆) -alkyl, benzyl or phenethyl;

and

R³is hydrogen or methyl.

The compounds of the formula I can be obtained by customary methods for preparing azo compounds, for example by diazotisation of amines of the formula III

D-NH₂(III)

Wherein D is as defined above, and wherein,

and coupling to compounds of the formula IV

Wherein R is¹、R²、R³、R⁴、R⁵And R⁷As defined above.

Typically, the amine of formula (III) may be diazotized at a temperature of-10 ℃ to 10 ℃ in an acidic medium such as acetic acid, propionic acid, or hydrochloric acid using a nitrosating agent such as nitrososulfuric acid, sodium nitrite, or methyl nitrite. Coupling to the compound of formula (IV) can be accomplished by adding the diazotized amine to the compound of formula (IV) under conditions described in the literature and known to those skilled in the art. After coupling, the compound of formula (I) may be recovered from the reaction mixture by any convenient method, such as filtration. The compounds of the formulae (III) and (IV) are known and can be obtained by methods described in the literature or known to the person skilled in the art.

The compounds of formula (I) are useful for dyeing and printing man-made fibre materials, especially polyester textiles with e.g. cellulosic materials like cotton and fibre blends thereof, which give these materials a colour with excellent wet fastness.

The dyeing of the mentioned fibre products with the dyes of the formula (I) can be carried out in a manner known per se, preferably from aqueous dispersions of the products, if appropriate in the presence of a carrier, at temperatures of between 80 and 110 ℃, by suction or by HT treatment at 110 to 140 ℃ in a dyeing autoclave, and by the so-called thermocuring process, in which the products are padded with the dyeing liquor and then fixed at temperatures of approximately 180 to 230 ℃. The mentioned fibre products can also be printed in a manner known per se by a process in which the dye of the formula (I) is incorporated into a printing paste and the paste-printed product is treated, if appropriate in the presence of a carrier, to fix the dye with HT steam, pressurised steam or dry heat at a temperature of from 180 to 230 ℃.

The dyes of the formula (I) should be present in the finest possible dispersions in the dyebaths and printing pastes used in the abovementioned applications.

The fine dispersion of the dye is carried out in a manner known per se by the following steps: the dye obtained in the preparation process is suspended in a liquid medium, preferably water, together with a dispersant, and the mixture is subjected to shear forces, the initially present particles being mechanically comminuted to such an extent that an optimum specific surface area is achieved and the sedimentation of the dye should be as low as possible. The particle size of the dye is generally from 0.5 to 5m, preferably about 1 m.

The dispersants used may be nonionic or anionic. Nonionic dispersants are, for example, the reaction products of alkylene oxides, such as ethylene oxide or propylene oxide, with alkylatable compounds, such as fatty alcohols, fatty amines, fatty acids, phenols, alkylphenols and carboxylic acid amines. Anionic dispersants are, for example, lignosulfonates, alkyl-or alkylaryl sulfonates or alkylaryl polyglycol ether sulfates. For most of the methods used, the dye preparations thus obtained should be pourable. In these cases, therefore, the dye and dispersant content is limited. Typically, the dispersion will have a dye content of up to 50 weight percent and a dispersant content of up to 25 weight percent. For economic reasons, the dye content is generally not less than 15% by weight.

The dispersion may also comprise other adjuvants, for example adjuvants which act as oxidizing or fungicidal agents. Such agents are well known in the art. The dye dispersions thus obtained can be used very advantageously for the preparation of printing pastes and dyebaths.

For certain fields of application, powder formulations are preferred. These powders contain dyes, dispersants and other auxiliaries, such as wetting agents, oxidizing agents, preservatives and dedusting agents.

A preferred method of preparation of the pulverulent dye preparations comprises removing the liquid from the liquid dye dispersions described above, for example by vacuum drying, freeze drying, by drying on a drum dryer, but preferably by spray drying.

Example 1

4- (4-Nitrophenylazo) -3-methyl-N-ethyl-N- (2-cyanomethoxy-carbonylethyl) aniline

A mixture of 4-nitroaniline (4.1 parts) and 86: 14(50 parts) acetic acid and propionic acid was stirred permanently at 5 ℃. Nitroso-sulfuric acid 40% (11.4 parts) was added below 5 ℃ and the mixture was stirred for 30 minutes. The obtained diazo solution is added stepwise to a stirred coupling mixture of N-ethyl, N- (2-cyanomethoxycarbonylethyl) -m-toluidine (7.3 parts), methanol (50 parts), water (200 parts) and sulphamic acid (1 part). After two hours, the product was isolated by filtration, washed with cold water and dried to yield 4- (4-nitrophenylazo) -3-methyl-N-ethyl-N- (2-cyanomethoxycarbonylethyl) aniline (6.5 parts). λ max 486nm (acetone)

When applied to polyester materials from aqueous dispersions, red shades are seen which have excellent resistance to moisture and light.

The dyes of the following examples of formula (laa) were prepared by the procedure of example 1 (see table 1).

TABLE 1

Examples	T	T	T	T	R	λmax(nm)
							2	-H	-H	-NO	-H	-CH	479
3	-H	-NO	-H	-H	-CH	468
							4	-NO	-H	-Cl	-H	-CH	508
5	-Cl	-H	-NO	-H	-CH	501
							6	-NO	-H	-Br	-H	-CH	507
7	-NO	-H	-Cl	-Cl	-CH	450
							8	-NO	-H	-Br	-Br	-CH	449
9	-NO	-H	-Cl	-Br	-CH	449
							10	-NO	-Cl	-H	-Cl	-CH	518
11	-NO	-H	-CN	-H	-CH	534
							12	-NO	-H	-CN	-Br	-CH	544
13	-NO	-H	-CN	-Cl	-CH	545
							14	-NO	-H	-NO	-H	-CH	535
15	-NO	-H	-Br	-NO	-CH	542
							16	-NO	-H	-Cl	-NO	-CH	544
17	-NO	-H	-CN	-CN	-CH	582
							18	-NO	-H	-CN	-NO	-CH	590
19	-NO	-H	-H	-H	-CH	490

Examples	T	T	T	T	R	λmax(nm)
							20	-NO	-H	-Cl	-H	-CH	513
21	-NO	-H	-Cl	-Cl	-CH	453
							22	-NO	-H	-Cl	-Br	-CH	453
23	-NO	-H	-Br	-Br	-CH	452
							24	-NO	-H	-CN	-H	-CH	539
25	-NO	-H	-NO	-H	-CH	540
							26	-NO	-H	-CN	-Br	-CH	549
27	-NO	-H	-CN	-Cl	-CH	548
							28	-NO	-H	-Br	-NO	-CH	548
29	-NO	-H	-Cl	-NO	-CH	549
							30	-H	-H	-NO	-H	-CH	483
31	-NO	-H	-CN	-CN	-CH	586
							32	-NO	-H	-H	-H	-CH[CH]	479
33	-NO	-H	-NO	-H	-CH[CH]	530
							34	-H	-H	-NO	-H	-CH[CH]	470
35	-H	-NO	-H	-H	-CH[CH]	460
							36	-NO	-H	-Cl	-H	-CH[CH]	498
37	-NO	-H	-Cl	-Cl	-CH[CH]	446
							38	-NO	-H	-Br	-Br	-CH[CH]	445
39	-NO	-H	-Br	-Cl	-CH[CH]	444
							40	-NO	-H	-CN	-H	-CH[CH]	528
41	-NO	-H	-CN	-Br	-CH[CH]	539
							42	-NO	-H	-CN	-Cl	-CH[CH]	539
43	-NO	-H	-Br	-NO	-CH[CH]	538
							44	-NO	-H	-Cl	-NO	-CH[CH]	537

Examples	T	T	T	T	R	λmax(nm)
							45	-NO	-H	-CN	-NO	-CH[CH]	580
46	-NO	-H	-CN	-CN	-CH[CH]	577
							47	-NO	-H	-H	-H	-CH	487
48	-NO	-H	-Cl	-H	-CH	509
							49	-NO	-H	-Cl	-Cl	-CH	452
50	-NO	-H	-Cl	-Br	-CH	451
							51	-NO	-H	-Br	-Br	-CH	452
52	-NO	-H	-CN	-H	-CH	536
							53	-NO	-H	-NO	-H	-CH	537
54	-NO	-H	-CN	-Br	-CH	546
							55	-NO	-H	-CN	-Cl	-CH	548
56	-NO	-H	-Br	-NO	-CH	544
							57	-NO	-H	-Cl	-NO	-CH	545
58	-H	-H	-NO	-H	-CH	480
							59	-NO	-H	-CN	-CN	-CH	584
60	-NO	-H	-Cl	-H	-CH	504
							61	-NO	-H	-CN	-H	-CH	529
62	-NO	-H	-Cl	-CN	-CH	543
							63	-NO	-H	-Br	-CN	-CH	542
64	-NO	-H	-Br	-NO	-CH	539

Example 65

4- (2, 6-dichloro-4-nitrophenylazo) -N-ethyl-N- (2-cyanomethoxy-carbonylethyl) aniline

A mixture of 2, 6-dichloro-4-nitroaniline (6.2 parts) and 86: 14(40 parts) of acetic acid and propionic acid was stirred permanently at 5 ℃. Nitroso-sulfuric acid 40% (11.4 parts) was added below 5 ℃ and the mixture was stirred for 30 minutes. The diazo solution is added stepwise to a stirred coupling mixture of N-ethyl, N-2 (cyanomethoxycarbonylethyl) -aniline (8.3 parts), methanol (50 parts), water (300 parts) and sulphamic acid (1 part). After one hour, the product was isolated by filtration, washed with cold water and dried to yield 4- (2, 6-dichloro-4-nitrophenylazo) -N-ethyl-N- (2-cyanomethoxycarbonylethyl) aniline (9.5 parts). λ max 432nm (acetone)

When applied to polyester materials from aqueous dispersions, a tan shade with excellent resistance to moisture and light is seen.

The dyes of the following examples of formula (lba) (see table 2) were prepared by the procedure of example 65.

TABLE 2

Examples	T	T	R	λmax(nm)
					66	-Cl	-Cl	-CH	433
67	-Cl	-Cl	-CH	434
					68	-Cl	-Cl	-CH[CH]	420
69	-Cl	-Cl	-CH	425
					70	-Cl	-Br	-CH	430
71	-Cl	-Br	-CH	431
					72	-Cl	-Br	-CH	433
73	-Cl	-Br	-CH[CH]	420
					74	-Cl	-Br	-CH	424
75	-Br	-Br	-CH	430
					76	-Br	-Br	-CH	432
77	-Br	-Br	-CH	431
					78	-Br	-Br	-CH[CH]	421
79	-Br	-Br	-CH	424

Example 80

4- (6-nitrobenzothiazol-yl-azo) -3-methyl-N-ethyl-N- (2-cyanomethoxyethyl) aniline

A mixture of 2-amino-6-nitrobenzothiazole (3.9 parts) and 86: 14(40 parts) of acetic acid and propionic acid was stirred permanently at 5 ℃. Nitroso-sulfuric acid 40% (7.6 parts) was added below 5 ℃ and the mixture was stirred for 1 hour. The diazo solution is added stepwise to a stirred coupling mixture of N-ethyl, N- (2-cyanomethoxycarbonylethyl) -m-toluidine (5.9 parts), methanol (25 parts), water (200 parts) and sulphamic acid (0.5 part). After one hour the product was isolated by filtration, washed with cold water and dried to yield 4- (6-nitrobenzothiazol-yl-azo) -3-methyl-N-ethyl-N- (2-cyanomethoxycarbonylethyl) aniline (2.4 parts) λ max ═ 545nm (acetone)

When applied to polyester materials from aqueous dispersions, excellent wet and light-fast ruby colorations are seen.

The following examples of formula (lab)

The dyes of the following examples of formula (lab) were prepared by the procedure of example 80 (see table 3).

TABLE 3

Example 107

4- (3, 5-dinitrothiophen-yl-azo) -3-methyl-N-ethyl-N- (2-cyanomethoxyethyl) aniline

A mixture of 2-amino-3, 5-dinitrothiophene (3.1 parts) and 86: 14(50 parts) of acetic acid and propionic acid is stirred permanently at 5 ℃. Nitroso-sulfuric acid 40% (5.7 parts) was added below 5 ℃ and the mixture was stirred for 30 minutes. The diazo solution is added stepwise to a stirred coupling mixture of N-ethyl, N- (2-cyanomethoxycarbonylethyl) -m-toluidine (4.0 parts), acetone (50 parts), water (300 parts) and sulphamic acid (0.5 part). After one hour the product was isolated by filtration, washed with cold water and dried to yield 4- (3, 5-dinitrothiophen-yl-azo) -3-methyl-N-ethyl-N- (2-cyanomethoxycarbonylethyl) aniline (3.0 parts) λ max ═ 640nm (acetone)

When applied to polyester materials from aqueous dispersions, excellent wet and light fastness blue shades are seen.

The dye of the following example of formula (lac) was prepared by the procedure of example 107 (see table 4).

TABLE 4

Examples	T	T	T	R	R	λmax(nm)
							108	-NO	-NO	-H	-H	-CH	620
109	-NO	-NO	-H	-H	-CH	625
							110	-NO	-NO	-H	-H	-CH	622
111	-NO	-NO	-H	-H	-CH[CH]	611
							112	-NO	-NO	-H	-CH	-CH	645
113	-NO	-NO	-H	-CH	-CH	640
							114	-NO	-NO	-H	-CH	-CH[CH]	632
115	-COOCH	-NO	-H	-CH	-CH	595
							116	-COOCH	-NO	-H	-H	-CH	583
117	-COCH	-NO	-H	-CH	-CH	599
							118	-COCH	-NO	-H	-CH	-CH	603
119	-COCH	-NO	-H	-H	-CH	585
							120	-CN	-NO	-H	-CH	-CH	604
121	-CN	-NO	-H	-CH	-CH[CH]	595
							122	-CN	-CHO	-Cl	-CH	-CH	585
123	-CN	-CHO	-Cl	-CH	-CH	591
							124	-CN	-CHO	-Cl	-H	-CH	579
125	-COOCH	-NO	-H	-H	-CH[CH]	565
							126	-COOCH	-NO	-H	-CH	-CH	601

Example 127

4- (5-Nitrobenzisothiazol-yl-azo) -3-methyl-N-ethyl-N- (2-cyanomethoxycarbonylethyl) aniline

7-amino-5-nitrobenzoisothiazole (2.9 parts) was added to a stirred mixture of 98% sulfuric acid (15 parts) and 4 parts phosphoric acid at room temperature. The mixture was heated to 55 ℃ and stirred at room temperature for 30 minutes. Nitroso-sulfuric acid 40% (6.1 parts) was added below 5 ℃ and the mixture was stirred for 2 hours.

The diazo solution is added stepwise to a stirred coupling mixture of N-ethyl, N- (2-cyanomethoxycarbonylethyl) -m-toluidine (4.8 parts), acetone (50 parts), water (100 parts) and sulphamic acid (0.5 part). Sodium acetate was added to increase the pH to 4.0 and the mixture was stirred for 1 hour. The product was isolated by filtration, washed with cold water and dried to yield 4- (5-nitrophenylisothiazol-yl-azo) -3-methyl-N-ethyl-N- (2-cyanomethoxycarbonylethyl) aniline (2.4 parts) λ max ═ 601nm (acetone)

When applied to polyester materials from aqueous dispersions, excellent wet and light fastness blue shades are seen.

The following examples of the formula (lad)

The dyes of the following examples of formula (lad) were prepared by the procedure of example 127 (see Table 5).

TABLE 5

Examples	R	R	λmax(nm)
				128	-H	-CH	588
129	-H	-CH[CH]	578
				130	-H	-CH	589
131	-CH	-CH	603
				132	-CH	-CH[CH]	593
133	-CH	-CH	608

Example 134

4- (5-Nitro-thiazol-yl-azo) -N-butyl-N- (2-cyano-methoxy-carbo-ethyl) aniline

A mixture of 2-amino-5-nitrothiophene (2.9 parts) and 86: 14(50 parts) of acetic acid and propionic acid is stirred permanently at 5 ℃. Nitroso-sulfuric acid 40% (7.0 parts) was added below 5 ℃ and the mixture was stirred for 30 minutes. The diazo solution is added stepwise to a stirred coupling mixture of N-butyl, N-2 (cyanomethoxycarbobutyl) -aniline (5.2 parts), acetone (50 parts), water (200 parts) and sulfamic acid (0.5 part). After one hour the product was isolated by filtration, washed with cold water and dried to yield 4- (5-nitrothiazol-yl-azo) -N-butyl-N- (2-cyanomethoxycarbonylethyl) aniline (2.9 parts) λ max ═ 571nm (acetone)

When applied to polyester materials from aqueous dispersions, blue shades are seen which are excellent in resistance to moisture and light.

The dyes of the following examples of formula (lae) (see table 6) were prepared by the procedure of example 134.

TABLE 6

Examples	R	R	λmax(nm)
				135	-H	-CH[CH]	557
136	-CH	-CH	575
				137	-CH	-CH	582
138	-CH	-CH[CH]	569

Example 139

4- (2-chloro-4-nitrophenylazo) -3-acetylamino-N-ethyl-N- (2-cyanomethoxycarbonylethyl) -aniline

A mixture of 2-chloro-4-nitroaniline (3.5 parts) and 86: 14(40 parts) of acetic acid and propionic acid was stirred permanently at 5 ℃. Nitroso-sulfuric acid 40% (7.0 parts) was added below 5 ℃ and the mixture was stirred for 30 minutes. The diazo solution is added stepwise to a stirred coupling mixture of 3 (N-ethyl, N-cyanomethoxycarbonylethyl) -amino-acetanilide (6.3 parts), methanol (40 parts), water (200 parts) and sulphamic acid (1 part). After two hours, the product was isolated by filtration, washed with cold water and dried to yield 4- (2-chloro-4-nitrophenylazo) -3-acetylamino-N-ethyl-N- (2-cyanomethoxy-carbonylethyl) -aniline (4.1 parts). λ max 525nm (acetone)

When applied to polyester materials from aqueous dispersions, ruby shades having excellent wet and light fastness are seen.

The dyes of the following examples of formula (lea) were prepared by the procedure of example 139 (see table 7).

TABLE 7

Example 157

4- (2-cyano-4-nitrophenylazo) -3-methyl-N-ethyl-N- (4-cyanomethoxycarbonylbutyl) -aniline

A mixture of 2-cyano-4-nitroaniline (3.2 parts) and 86: 14(50 parts) of acetic acid and propionic acid was stirred permanently at 5 ℃. Nitroso-sulfuric acid 40% (7.6 parts) was added below 5 ℃ and the mixture was stirred for 30 minutes. The diazo solution is added stepwise to a stirred coupling mixture of N-ethyl, N- (4-cyanomethoxycarbonylbutyl) -m-toluidine (6.0 parts), methanol (50 parts), water (200 parts) and sulphamic acid (1 part). After two hours, the product was isolated by filtration, washed with cold water and dried to yield 4- (2-cyano-4-nitrophenylazo) -3-methyl-N-ethyl-N- (4-cyanomethoxycarbonylbutyl) -aniline. (5.3 parts) λ max ═ 548nm (acetone)

When applied to polyester materials from aqueous dispersions, excellent wet and light-fast ruby colorations are seen.

The dye of the following example of formula (laf) (see Table 8) was prepared by the procedure of example 157.

TABLE 8

Example 169

4- (2-cyano-4-nitrophenylazo) -3-methyl-N-ethyl-N- (2- (1-cyanoethoxy) carbonylethyl) -aniline

A mixture of 2-cyano-4-nitroaniline (2.1 parts) and 86: 14(40 parts) of acetic acid and propionic acid is stirred permanently at 5 ℃. Nitroso-sulfuric acid 40% (4.9 parts) was added below 5 ℃ and the mixture was stirred for 30 minutes. The diazo solution is added stepwise to a stirred coupling mixture of N-ethyl, N- (2- (1-cyanomethoxy) carbonylethyl) -m-toluidine (3.7 parts), acetone (50 parts), water (300 parts) and sulfamic acid (1 part). After two hours, the product was isolated by filtration, washed with cold water and dried to yield 4- (2-cyano-4-nitrophenylazo) -3-methyl-N-ethyl-N- (2- (1-cyanoethoxy) carbonylethyl) -aniline (3.5 parts) λ max ═ 534nm (acetone)

When applied to polyester materials from aqueous dispersions, excellent wet and light-fast ruby colorations are seen.

The dye of the following example of formula (lda) (see Table 9) was prepared by the procedure of example 169.

TABLE 9

Example 194

4- (2-chloro-4-nitrophenylazo) -N-ethyl-N- (2-cyanomethoxycarbonylpropyl) -aniline

A mixture of 2-chloro-4-nitroaniline (parts) and 86: 14(40 parts) acetic acid and propionic acid was stirred permanently at 5 ℃. Nitroso-sulfuric acid 40% (4.9 parts) was added below 5 ℃ and the mixture was stirred for 30 minutes. The diazo solution is added stepwise to a stirred coupling mixture of N-ethyl, N- (2-cyanomethoxycarbonylpropyl) -m-toluidine (parts), acetone (50 parts), water (300 parts) and sulphamic acid (1 part). After two hours, the product was isolated by filtration, washed with cold water and dried to yield 4- (2-chloro-4-nitrophenylazo) -N-ethyl-N- (2-cyanomethoxycarbonylpropyl) -aniline (3.5 parts) λ max ═ 534nm (acetone)

When applied to polyester materials from aqueous dispersions, red shades are seen which have excellent resistance to humidity and light.

The dye of the following example of formula (lca) (see Table 10) was prepared by the procedure of example 194.

Watch 10

Example 213

4- (4-Nitrophenylazo) -N-ethyl-N- (2 (1-cyanoethoxy) carbonylpropyl) -phenylamine

4-nitroaniline (2.0 parts) was stirred permanently at 5 ℃ with a 86: 14(50 parts) mixture of acetic acid and propionic acid. Nitroso-sulfuric acid 40% (5.7 parts) was added below 5 ℃ and the mixture was stirred for 30 minutes. The diazo solution is added stepwise to a stirred coupling mixture of N-ethyl, N- (2- (1-cyanomethoxy) carbonylpropyl) -aniline (4.7 parts), acetone (50 parts), water (200 parts) and sulfamic acid (1 part). After two hours, the product was isolated by filtration, washed with cold water and dried to yield 4- (4-nitrophenylazo) -N-ethyl-N- (2- (1-cyanoethoxy) carbonylpropyl) -aniline (2.9 parts) λ max ═ 473nm (acetone)

When applied to polyester materials from aqueous dispersions, scarlet shades are seen which are excellent in resistance to moisture and light.

The dyes of the following examples of the formula (lh) were prepared by the procedure of example 213 (see Table 11).

Example 225

4- (2-cyano-4-nitrophenylazo) -N-ethyl-N- (1-cyanomethoxycarbonylethyl) -m-toluidine

A mixture of 2-cyano-4-nitroaniline (3.1 parts) and 86: 14(40 parts) of acetic acid and propionic acid was stirred permanently at 5 ℃. Nitroso-sulfuric acid 40% (6.6 parts) was added below 5 ℃ and the mixture was stirred for 30 minutes. The diazo solution is added stepwise to a stirred coupling mixture of N-ethyl, N- (1- (cyanomethoxycarbonylethyl) -m-toluidine (4.1 parts), methanol (40 parts), water (200 parts) and sulfamic acid (1 part) after two hours the product is isolated by filtration, washed with cold water and dried to yield 4- (2-cyano-4-nitrophenylazo) -N-ethyl-N- (1-cyanomethoxycarbonylethyl) -m-toluidine (3.9 parts) λ max ═ 510nm (acetone)

When applied to polyester materials from aqueous dispersions, excellent wet and light fastness red shades are seen.

Claims (10)

1. A dye of the formula I

Wherein

D is a radical of the formula (IIa) or (IIb) or (IIc) or (IId) or (IIe)

Wherein

T¹、T²And T³Independently hydrogen, halogen or nitro;

T⁴is hydrogen, halogen, cyano or nitro;

wherein T is¹、T²、T³And T⁴At least one of which is not hydrogen;

wherein

T⁵Is hydrogen or halogen; and

T⁶is hydrogen, -SO₂CH₃-SCN or nitro;

wherein T is⁵And T⁶At least one of which is not hydrogen;

wherein T is⁷Is nitro, -CHO or formula

In which T is¹⁰is-H, halogen, nitro and cyano;

T⁸is hydrogen or halogen; and

T⁹is nitro, cyano or-COCH₃or-COOT¹⁰Wherein T is¹⁰Is (C)₁-C₄) -an alkyl group;

R¹is hydrogen, (C)₁-C₄) -alkyl or-NHCOR⁶Wherein R is⁶Is (C)₁-C₄) -alkyl or phenyl;

R²is unsubstituted (C)₁-C₆) Alkyl, by hydroxy, (C)₁-C₄) Alkoxy-or halogen-substituted (C)₁-C₆) -alkyl, benzyl, or phenethyl;

R³is hydrogen or methyl;

R⁴is hydrogen or methyl;

R⁵is hydrogen, methyl or phenyl;

R⁷is hydrogen, chlorine, methoxy or ethoxy;

n is 0, 1 or 2;

s is 0 or 1;

provided that

At R¹、R³、R⁴、R⁵And R⁷Is hydrogen and n is 0

D is a radical of the formula (IIc), (IId), (IIe) or (IIa), in which T¹Not being nitro radicals

If T is²、T³And T⁴Is a hydrogen atom, and is,

if T is²And T³Is hydrogen and T⁴Is chloro or cyano and

if T is²And T⁴Is hydrogen and T³Is chlorine; and

further provided that

R²Is unsubstituted (C)₁-C₆) -alkyl if R¹Is methyl, R³、R⁴、R⁵And R⁷Is hydrogen and n ═ 0.

2. A dye of formula (Ia) according to claim 1

Wherein

D is a radical of the formula (IIa), (IIb), (IIc), (IId) or (IIe);

R¹is (C)₁-C₄) -an alkyl group;

R²is unsubstituted (C)₁-C₆) -alkyl, benzyl or phenethyl; and

n is 0, 1 or 2.

3. A dye of the formula (Ib) according to claim 1

Wherein

T³' is bromine or chlorine; and

R²is unsubstituted (C)₁-C₆) Alkyl, by hydroxy, (C)₁-C₄) Alkoxy-or halogen-substituted (C)₁-C₆) -alkyl, benzyl, or phenethyl.

4. A dye of the formula (Ic) according to claim 1

Wherein

D is a radical of the formula (IIa), (IIb), (IIc), (IId) or (IIe);

R¹is hydrogen, (C)₁-C₄) -alkyl or-NHCOR⁶Wherein R is⁶Is (C)₁-C₄) -alkyl or phenyl;

R²is unsubstituted (C)₁-C₆) Alkyl, by hydroxy, (C)₁-C₄) Alkoxy-or halogen-substituted (C)₁-C₆) -alkyl, benzyl, or phenethyl; and

R³is hydrogen and R⁴Is methyl or R³Is methyl and R⁴Is hydrogen.

5. Dyes of formula (Id) according to claim 1

Wherein

D is a radical of the formula (IIa), (IIb), (IIc), (IId) or (IIe);

R¹is hydrogen, (C)₁-C₄) -alkyl or-NHCOR⁶Wherein R is⁶Is (C)₁-C₄) -alkyl or phenyl;

R²is unsubstituted (C)₁-C₆) Alkyl, by hydroxy, (C)₁-C₄) Alkoxy-or halogen-substituted (C)₁-C₆) -alkyl, benzyl, or phenethyl; and

R⁵is methyl or phenyl.

6. A dye of the formula (Ie) according to claim 1

Wherein

D is a radical of the formula (IIa), (IIb), (IIc), (IId) or (IIe);

R²is unsubstituted (C)₁-C₆) Alkyl, by hydroxy, (C)₁-C₄) Alkoxy-or halogen-substituted (C)₁-C₆) -alkyl, benzyl, or phenethyl;

R⁶is (C)₁-C₄) -alkyl or phenyl;

R⁷is chloro, methoxy or ethoxy; and

n is 0, 1 or 2.

7. A dye of formula (If) according to claim 1

Wherein

R²Is unsubstituted (C)₁-C₆) Alkyl, by hydroxy, (C)₁-C₄) Alkoxy-or halogen-substituted (C)₁-C₆) -alkyl, benzyl, or phenethyl;

R⁸is a nitro group; and

n is 0, 1 or 2.

8. Dyes of formula (Ig) according to claim 1

Wherein

D is a radical of the formula (IIa), (IIb), (IIc), (IId) or (IIe);

R¹is hydrogen, (C)₁-C₄) -alkyl or-NHCOR⁶Wherein R is⁶Is (C)₁-C₄) -alkyl or phenyl;

R²is unsubstituted (C)₁-C₆) Alkyl, by hydroxy, (C)₁-C₄) Alkoxy-or halogen-substituted (C)₁-C₆) -alkyl, benzyl, or phenethyl;

and

R³is hydrogen or methyl.

9. A process for the preparation of a dye according to any one of claims 1 to 8, comprising diazotisation of an amine of formula III and coupling to a compound of formula IV:

D-NH₂(III)

wherein D is as defined in the preceding claims,

wherein R is¹、R²、R³、R⁴、R⁵And R⁷As defined in the preceding claims.

10. Use of a dye according to any one of claims 1 to 8 for dyeing and printing synthetic fibre materials and fibre blends thereof.